Reaction product of rosin, aromatic amines and furfural



Patented Jan. 17, 1933 UNITED STATES PATENT OFFICE OSCAR A. CHERRY ANDFRANZ KURATH, OF CHICAGO, ILLINOIS, ASSIGNORS TO ECONOMY FUSE &MANUFACTURING COMPANY, OF CHICAGO, ILLINOIS, A CORPORA- 'I'ION OF YORKREACTION PRODUCT OF ROSIN, ABOMATIC AMINES AND FURFURAL No Drawing.Original application filed March 80, 1928, Serial No. 266,114. Dividedand this application filed August 16, 1929. Serial No. 886,485.

This invention relates to a novel composition of matter and to theprocess of producing same, and more particularly to the composition ofmatter and process characterized by reacting, in a-manner to bhereinafter set forth, aldehydes, orgaruc acids and amides.

This a plication is a division of the applicants atent No. 1,800,815,dated April 14th, 1931, and the specification appearing herein is theexact copy of the specification of said patent. This invention, however,relates .to that aspect of the former disclosure which has to do withthe composition of matter which is the reaction product of rosin,aromatic amines and aldehydes.

It is known that organic acids will react with aromatic amines to formsubstances I which in some cases are amorphous and in other casescrystalline bodies. Some of the crystalline bodies so formed possessproperties which render them useful in the arts for various purposes,whereas the amorphous substances referred to or those bodies which arediliicultly crystallizable, have received no extended commercialapplication.

It is further known that aldehydes, such as, for instance, formaldehydeorfurfural, will react with aromatic amines under favorable conditionsto form amorphous or resinous bodies, which resinous bodies or sub-.

stances have been of only little use commercially.

It has now been found that by reacting with aldehydes on the reactionproducts of certain carboxylic acids and aromatic primary amines thatproducts possessing conenough to include the combinations of thesesubstances may be selected resulting in the production of slightlydifi'erent products, but it is to be understood that the invention is tobe construed broadly group of products produced by reacting thesubstances in a general manner falling within the scope of thisinvention, it being, of course, understood that amine, or diiferentaldehydes may be used 'to I react with a particular acid amine reactionproduct. It is also within the contemplation of the present invention toemploy instead of pure compounds, a mixture of one or more of thecompounds enumerated, such as, for instance, mixtures of differentacids, amines or aldehydes in any desirable combination for the purposeof obtaining the particular properties desired in the final product.

It has also been found, as will be hereinafter more, particularlypointed out, that some of the products falling within the groupcontemplated in the present invention, 7

are waxy substances'possessing many of the physical propertiesbf naturalwaxes;

Accordingly, it is one of the objects of the present invention toprovide a new composition of matter or group of substances possessingnew and useful properties.

It is a further object of this invention to provide a new and usefulgroup of products or compositions of matter, which are reaction productsof aldehydes, acids and amines.

It is a further object of this invention to provide agroup of productswhich are in a general way chemically, similar in nature, but whichpossess slightly varying properties according to the combination ofaldehydes, acids and amines selected for their production.

' It is a further object of this-invention to Wei provide a group ofproducts, some of which are waxy substances possessing many of thephysical properties of natural waxes.

It is also an object of this invention to provide a group of substances,some. of which possess properties rendering them suitable for use asplasticizing agents for potentially reactive phenolic condensationproducts in hot molding operations;

It is a further object of this invention to provide a group ofsubstances, some of which possess properties suitable for use asplasticizing agents as above set forth, which will possess either theproperty of a plasticizing agent, or a lubricant for use in hot moldingoperations, or of a substance for darkening molding phenoliccondensation products, or-

any combination, or all of these properties.

Various other objects of this invention will appear as the descriptionproceeds.

In order that the invention may be more readily understood, variousexamples will be given herein of the process and product contemplatedand inasmuch as a variety of each of the substances or compounds, viz.,the aldehydes, acids and amine, is contemplated in practicing thepresent invention, it is deemed advisable to group these and treat themseparately as typical examples. I

Irrespective of the particular selection of compounds, it is to beunderstood that in all cases the aldehyde is reacted with the reactionproduct of the acid and amine, or, in other words, the acid and amineare reacted initially and the product thereof is subsequently reactedwith the aldehyde.

The first group of examples are those in which various aldehydes areused. The first example of the group is as follows In a flask equippedwith a return condenser, 56.8 parts by weight of stearic acid and 18.6parts by ght of aniline are heated to substantially from 170 to 200 C.for approximately one hour. Water is formed as a result of the reactionbetween the organic acid and the amine. In order to eliminate the waterso formed, it is desirable to so arrange the condenser that the watermay escape, but so that any aniline being volatilized will be returnedto the flask. At the end of the heating period, and after some cooling,19 parts by weight of furfural are added and the whole is heated toabout 200 C. for approximately one-half hour. At this temperature theproduct is athin liquid, which, upon cooling, solidifies to a Waxy. darkbrown solid at room temperature. The product so formed is a substitutefor natural waxes and is found suitable to re: place them in many oftheir applications, and is especially valuable for use in phenoliccondensation products, particularly hot molding compositions made frompotentially reactive phenolic condensation products.

The product formed in accordance with the above process is found, whenused with hot molding compositions as above referred to, to have athree-fold function. The waxy product first serves to lubricate thecomposition in such a manner as to prevent sticking of the compositionto the steel molds in which these compositions are ordinarily molded.This is a decidedly valuable property especially in connection withcertain compositions made in part from furfural, which compositions havea tendency to stick to the mold during hot pressing operations. Theabove product secondly serves to plasticize the phenolic hot moldingcompositions, causing the materials to flow more readily during themolding operations; and, thirdly, they serve in such compositions todarken to some extent the final product.

A second example which is somewhat similar to that above given, with theexception that the furfural is replaced by formaldehyde, produces aproduct somewhat similar to that above described, with the exceptionthat it does not affect the color of the products in which it isdissolved or mixed, but generally speaking, it may be used in the sameway as the furfural product, it possessing the lubricating andplasticizing proper ties. This product is produced by replacing thefurfural in the above stated example by 15 parts by weight (37 70)commercial formaldehyde solution. On account of the water in theformaldehyde, the heat treating temperature is necessarily less, andabout one hour is usually required to effect complete combination of thealdehyde. The product so obtained is similar to the furfural product,but is a trifle more brittle and is light in color.

A condensing agent, as for example a mineral acid, may be employed toaccelerate the reaction between the aldehyde and the amineacid compound.When furfural is the aldehyde employed, the use of an acid catalystserves to make the resultant composition of a very deep, black color.

The next examples which are to follow are those in which acids otherthan stearic acid are used with aniline in substantially the sameprocedure as that given above. The products which result from theemployment of the various acids are found to possess slightly varyingproperties, depending upon the acid selected, and to a lesser extentupon the aldehyde. For example, succinic acid may be employed in thereaction with aniline and furfural and is found to yield a black, 7 i

' acid alone.

product is somewhat tougher and more plastic than a similar product madefrom stearic By reducing the proportions of benzoic acid in the abovemixture, the hardness and the wax-like nature of the product isincreased, oleic acid, aniline and furfural yield a black, viscousoleaginousproduct. When the product of a mixture of oleic and stearicacids reacted upon aniline is reached upon with, furfural, a black,tough, waxy product is obtained.

A decidedly resinous substance is obtained by reacting 30 parts of rosinor colophony which is largely abietic acid or its anhydride upon 10parts of aniline for about three hours, and adding 9 parts of furfuralto the product and continuing the heat treatment. The reaction of therosin-aniline substance with formaldehyde is so violent that ifformalde-' hyde is to be reacted with this substance the solution is tobe added slowly in small increments. The rosin-amine-aldehyde product soformed is resinous as is rosin, but is less brittle than rosin. It has adecided plasticizing action on reactive phenolic molding compositions,such as are used in hot molding 0 rations. It is found that by replacinga out one-half of the rosin in the above reaction by stearic acid andforming a mixed acid-amine-aldehyde product, a substance possessing bothresinous and wax-like characteristics may be obtained.

The examples hereinafter given will be illustrative of the resultsobtained when various amines are employed. It is found in practice thatby using a diamine and by using mixtures of acids as well as singleacids, a variety of products may be obtained. The products are ingeneral harder at room temperatures than similar compounds made fromsimple amines. For example, a hard, waxlike product is obtained byreacting upon one gram mol of meta-phenylene-diamine with one gram molof benzoic acid and one gram mol of stearic acid, and treating theroduce with two gram mols of furfural. black, high melting wax-likesubstance, not quite so tough as that obtainable as above described, maybe made from one gram mol'of stearic acid, one gram mol ofmeta-phenylenediamine and one gram mol of fu-rfural. A lower meltingsubstance may be made by increasing the proportions of stearic acid inthe above example.

Other amines, such as toluidines and naphthylamines may be used. Thecarboxylic acids of high molecular weights, that is, those acidscontaining more than 6 carbon atoms are preferred, as acids of lowermolecular the very low molecular weight acids, as for example aceticacid, do not react with aniline to form a product which will easilyreact with aldehydes.

We claim:

1. A composition of matter formed by reacting furfural on the reactionproduct of rosin and an aromatic amine.

2. The process which consists in reacting the reaction product of rosinand an aromatic amine with furfural.

3. The process which consists in reacting rosin with a mixture of aplurality of aromatic amines and thenreacting the reaction productthereof with furfural.

4. The process which consists in reacting rosin with aromatic amines andthen reacting the reaction product thereof with furfuraland anotheraldehyde. 1

5. A composition of matter formed by reacting furfural with the reactionproduct of rosin and aniline.

Signed at Chicago, Illinois, this 12th day of August, 1929.

, OSCAR A. CHERRY.

FRANZ KURATH.

weight usually produce crystalline derivatives with aniline. Althoughthere is nothing objectionable per se in a crystalline intermediateproduct, useful products are generally more easily obtainable from acidsof higher molecular weight. In fact, some of

